Polymer, resist composition including the same, and method of forming pattern by using that resist composition

Abstract

To provide a polymer, a resist composition including the same, and a method of forming a pattern by using the same.SOLUTION: Provided are: a polymer including a first repeating unit represented by the chemical formula 1 in the figure; a resist composition including the polymer; and a method of producing a pattern using the resist composition. In the chemical formula 1, descriptions of L11 to L14, a11 to a13, A11, X11, R11, R12, b12 and p are as provided in the specification.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a polymer, a resist composition containing the polymer, and a pattern forming method utilizing the resist composition. [Background technology]

[0002] In the manufacture of semiconductors, resists whose physical properties change in response to light are used to form fine patterns. Among them, chemically amplified resists have been widely used. Chemically amplified resists enable patterning by forming an acid by reacting light with a photoacid generator, which reacts again with a base resin and changes the solubility of the base resin in a developer.

[0003] In particular, when using high-energy rays having a relatively high energy such as EUV, there is a problem that the number of photons is significantly smaller even when irradiated with light of the same energy. Therefore, there is a demand for a resist composition that can effectively function even when used in a small amount and can provide improved sensitivity and / or resolution. Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a resist composition that can provide improved sensitivity and / or resolution, and a method of forming a pattern using the resist composition. [Means for solving the problem]

[0005] According to one aspect, there is provided a polymer comprising a first repeating unit represented by Formula 1:

[0006] [ka]

[0007] In the above Chemical Formula 1, L 11 ~L 13 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or C which optionally contains a heteroatom. 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of L 14 C, which may optionally contain heteroatoms 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of a11 to a13 each independently represent an integer of 1 to 4, A 11 is C 6 -C 30 Aromatic group or C 1 -C 30 is a heteroaromatic group, R 11 and R 12 are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which may optionally contain a heteroatom. 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of b12 is selected from integers from 1 to 10; X 11 is OH, SH or NH 2 and p is selected from an integer of 1 to 5; * indicates a bonding site with an adjacent atom.

[0008] In another aspect, there is provided a resist composition comprising the aforementioned polymer, a photoacid generator, and an organic solvent.

[0009] In still another aspect, there is provided a pattern forming method including the steps of applying the resist composition to form a resist film, exposing at least a portion of the resist film to high-energy radiation, and developing the exposed resist film using a developer. Effect of the Invention

[0010] Embodiments of the present invention can provide resist compositions that can provide improved sensitivity and / or resolution. [Brief description of the drawings]

[0011] [Figure 1] 1 is a flow chart illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2A] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2B] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2C] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 3A] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3B] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3C] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3D] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3E] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3F] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3G] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3H]1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3I] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 3J] 1 is a graph showing normalized residual film thickness versus exposure dose evaluated in Evaluation Example 1. [Figure 4A] 1A-1D are side cross-sectional views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4B] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4C] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4D] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4E] 1A-1D are side cross-sectional views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 5A] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 5B] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 5C] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 5D] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 5E] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention can be modified in various ways and can have various embodiments, and a specific embodiment will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to a specific embodiment, and the present invention should be understood to include all modifications, equivalents, or alternatives included in the spirit and technical scope of the present invention. When a detailed description of a known technology related to the description of the present invention is considered to make the gist of the present invention unclear, the detailed description will be omitted.

[0013] Terms such as "first," "second," and "third" are used to describe various components, but are used only for the purpose of distinguishing one component from other components, and do not limit the order, types, etc. of the components.

[0014] In this specification, when a layer, film, region, plate or other part is described as being "on" or "above" another part, this includes not only parts that are immediately in contact with each other and are above, below, to the left or right of each other, but also parts that are not in contact with each other and are above, below, to the left or right of each other.

[0015] The singular expression includes the plural expression unless the context clearly dictates otherwise. Terms such as "comprise" or "have" should be understood to indicate the presence of a feature, number, step, operation, component, part, ingredient, material, or combination thereof described in the specification, unless specifically stated to the contrary, and not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, ingredients, materials, or combinations thereof.

[0016] Whenever a range of values ​​is recited, the range includes all values ​​that fall within the range as expressly stated, and further includes the boundaries of the range, thus a range "from X to Y" includes all values ​​between X and Y, including X and Y.

[0017] In this specification, "C x -C y" means that the number of carbon atoms constituting the substituent is x to y. For example, "C 1 -C 6 " means that the number of carbon atoms constituting the substituent is 1 to 6, and "C 6 -C 20 " means that the number of carbon atoms constituting the substituent is 6 to 20.

[0018] In this specification, the term "monovalent hydrocarbon group" refers to a monovalent residue derived from an organic compound containing carbon and hydrogen or a derivative thereof, and specific examples include linear or branched alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); monovalent saturated cyclic aliphatic hydrocarbon groups (cycloalkyl groups) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl, and the like). monovalent unsaturated aliphatic hydrocarbon groups (alkenyl groups, alkynyl groups) (e.g., allyl groups); monovalent unsaturated cyclic aliphatic hydrocarbon groups (cycloalkenyl groups) (e.g., 3-cyclohexenyl); aryl groups (e.g., phenyl groups, 1-naphthyl groups, and 2-naphthyl groups); arylalkyl groups (e.g., benzyl groups and diphenylmethyl groups); heteroatom-containing monovalent hydrocarbon groups (e.g., tetrahydrofuranyl groups, methoxymethyl groups, ethoxymethyl groups, methylthiomethyl groups, acetamidomethyl groups, trifluoroethyl groups, (2-methoxyethoxy)methyl groups, acetoxymethyl groups, 2-carboxy-1-cyclohexyl groups, 2-oxopropyl groups, 4-oxo-1-adamantyl groups, and 3-oxocyclohexyl groups), or any combination thereof. In addition, in these groups, some of the hydrogens are replaced by moieties containing heteroatoms, such as oxygen, sulfur, nitrogen or halogen atoms, or some of the carbons are replaced by moieties containing heteroatoms, such as oxygen, sulfur or nitrogen, so that these groups can also contain a hydroxy group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate, a lactone ring, a sultone ring, a carboxylic acid anhydride moiety, or a haloalkyl moiety.

[0019] In the present specification, the term "divalent hydrocarbon group" refers to a divalent residue in which any one of the hydrogen atoms of a monovalent hydrocarbon group is replaced by a bonding site with an adjacent atom. The divalent hydrocarbon group may include, for example, a linear or branched alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, or groups in which some of the carbon atoms are replaced by heteroatoms.

[0020] As used herein, "alkyl group" means a linear or branched saturated aliphatic hydrocarbon monovalent group, specific examples of which include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, etc. As used herein, "alkylene group" means a linear or branched saturated aliphatic hydrocarbon divalent group, specific examples of which include methylene, ethylene, propylene, butylene, isobutylene, etc.

[0021] As used herein, the term "halogenated alkyl group" refers to an alkyl group in which one or more hydrogen atoms have been replaced with halogen. Specific examples include CF 3 etc.

[0022] As used herein, an "alkoxy group" is -OA 101 where A means a monovalent group having the formula 101 is an alkyl group. Specific examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group.

[0023] As used herein, an "alkylthio group" is defined as -SA 101 where A means a monovalent group having the formula 101 is an alkyl group.

[0024] In the present specification, the term "halogenated alkoxy group" refers to an alkoxy group in which one or more hydrogen atoms are replaced with halogen, and a specific example is -OCF 3 etc.

[0025] As used herein, the term "halogenated alkylthio group" refers to an alkylthio group in which one or more hydrogen atoms have been replaced with halogen. Specific examples include -SCF 3 etc.

[0026] In this specification, "cycloalkyl group" means a monovalent saturated hydrocarbon cyclic group, specific examples of which include monocyclic groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and condensed polycyclic groups such as a norbornyl group and an adamantyl group. In this specification, "cycloalkylene group" means a divalent saturated hydrocarbon cyclic group, specific examples of which include a cyclopentylene group, a cyclohexylene group, an adamantylene group, an adamantylmethylene group, a norbornylene group, a norbornylmethylene group, a tricyclodecanylene group, a tetracyclododecanylene group, a tetracyclododecanylmethylene group, a dicyclohexylmethylene group, and the like.

[0027] As used herein, a "cycloalkoxy group" is defined as -OA 102 where A means a monovalent group having the formula 102 is a cycloalkyl group. Specific examples thereof include a cyclopropoxy group, a cyclobutoxy group, and the like.

[0028] As used herein, a "cycloalkylthio group" is defined as -SA 102 where A means a monovalent group having the formula 102 is a cycloalkyl group.

[0029] As used herein, a "heterocycloalkyl group" refers to a cycloalkyl group in which some of the carbons are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen, and the heterocycloalkyl group may specifically contain an ether bond, an ester bond, a sulfonate ester bond, a carbonate, a lactone ring, a sultone ring, or a carboxylic anhydride moiety. As used herein, a "heterocycloalkylene group" refers to a cycloalkylene group in which some of the carbons are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0030] As used herein, a "heterocycloalkoxy group" is defined as -OA 103 where A means a monovalent group having the formula 103 is a heterocycloalkyl group.

[0031] As used herein, an "alkenyl group" refers to a linear or branched, unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon double bonds. As used herein, an "alkenylene group" refers to a linear or branched, unsaturated aliphatic hydrocarbon divalent group containing one or more carbon-carbon double bonds.

[0032] As used herein, an "alkenyloxy group" is -OA 104 where A means a monovalent group having the formula 104 is an alkenyl group.

[0033] As used herein, the term "cycloalkenyl group" refers to a monovalent unsaturated cyclic hydrocarbon group containing one or more carbon-carbon double bonds. As used herein, the term "cycloalkenylene group" refers to a divalent unsaturated cyclic hydrocarbon group containing one or more carbon-carbon double bonds.

[0034] In the present specification, the term "cycloalkenyloxy group" refers to a -OA 105 where A means a monovalent group having the formula 105 is a cycloalkenyl group.

[0035] As used herein, a "heterocycloalkenyl group" refers to a cycloalkenylene group in which some of the carbon atoms have been replaced with a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen. As used herein, a "heterocycloalkenylene group" refers to a cycloalkenylene group in which some of the carbon atoms have been replaced with a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0036] As used herein, a "heterocycloalkenyloxy group" is defined as -OA 106 where A means a monovalent group having the formula 106 is a heterocycloalkenyl group.

[0037] As used herein, "alkynyl group" means a linear or branched unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon triple bonds.

[0038] As used herein, an "alkynyloxy group" is defined as -OA 107 where A means a monovalent group having the formula 107 is an alkynyl group.

[0039] In this specification, an "aryl group" means a carbocyclic aromatic monovalent group, and specific examples include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a chrysenyl group.

[0040] As used herein, an "aryloxy group" is -OA 108 where A means a monovalent group having the formula 108 is an aryl group.

[0041] As used herein, a "heteroaryl group" refers to a heterocyclic aromatic monovalent group, and specific examples include pyridinyl groups, pyrimidinyl groups, pyrazinyl groups, etc. As used herein, a "heteroarylene group" refers to a divalent group having a heterocyclic aromatic system.

[0042] As used herein, a "heteroaryloxy group" is defined as -OA109 where A means a monovalent group having the formula 109 is a heteroaryl group.

[0043] In the present specification, the term "substituent" refers to a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carbonyl group, a carboxylic acid group, an amino group, an ether moiety, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, a C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C 20 Heteroaryloxy group, or C 1 -C 20 Heteroarylthio groups; Deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether moiety, ester moiety, sulfonic acid ester moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C substituted with heteroarylthio groups, and any combination thereof 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 6 -C 20Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 heteroarylthio groups; and any combination thereof.

[0044] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the description with reference to the drawings, substantially the same or corresponding components are given the same drawing numbers, and duplicated description thereof will be omitted. In the drawings, thicknesses of a plurality of layers and regions are exaggerated to clearly express them. In the drawings, thicknesses of some layers and regions are exaggerated for convenience of description. Meanwhile, the embodiments described below are merely examples, and various modifications are possible from such embodiments.

[0045] [polymer] The polymer according to an exemplary embodiment includes a first repeating unit represented by Formula 1: [ka]

[0046] In Chemical Formula 1, L 11 ~L 13 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or C which optionally contains a heteroatom. 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of L 14 C, which may optionally contain heteroatoms 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of a11 to a13 each independently represent an integer of 1 to 4, A 11is C 6 -C 30 Aromatic group or C 1 -C 30 is a heteroaromatic group, R 11 and R 12 are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which optionally contains a heteroatom. 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of b12 is selected from integers from 1 to 10; X 11 is OH, SH or NH 2 and p is selected from an integer of 1 to 5; * indicates a bonding site with an adjacent atom.

[0047] In one embodiment, L in Formula 1 11 ~L 13 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); a substituted or unsubstituted C 1 -C 30 Alkylene group; substituted or unsubstituted C 3 -C 30 Cycloalkylene group; substituted or unsubstituted C 3 -C 30 Heterocycloalkylene group; substituted or unsubstituted C 2 -C 30 Alkenylene group; substituted or unsubstituted C 3 -C 30 Cycloalkenylene group; substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene group; substituted or unsubstituted C 6 -C 30 arylene group; or substituted or unsubstituted C 1 -C 30It is a heteroarylene group.

[0048] In one embodiment, L in Formula 1 11 ~L 13 are each independently a single bond; O; C(=O); C(=O)O; OC(=O); and deuterium, a halogen, a cyano group, a hydroxyl group, an amino group, a carboxylic acid group, a thiol group, an ester moiety, a sulfonic acid ester moiety, a carbonate moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 6 -C 20 aryl groups, or any combination thereof, substituted or unsubstituted, 1 -C 20 Alkylene group, C 3 -C 20 Cycloalkylene group, C 3 -C 20 Heterocycloalkylene group, C 2 -C 20 Alkenylene group, C 3 -C 20 Cycloalkenylene group, C 3 -C 20 Heterocycloalkenylene group, C 6 -C 20 Arylene groups, and C 1 -C 20 heteroarylene groups;

[0049] In one embodiment, L in Formula 1 11 ~L 13 are each independently a single bond; O; C(=O); C(=O)O; OC(=O); and deuterium, halogen, C 1 -C 20 Alkyl group, C 1-C 20 Halogenated alkyl groups, C 1 -C 20 C, substituted or unsubstituted with alkoxy, phenyl, naphthyl, or any combination thereof 1 -C 20 Alkylene group, C 3 -C 20 Cycloalkylene group, C 3 -C 20 heterocycloalkylene groups, phenylene groups, and naphthylene groups.

[0050] In one embodiment, L in Formula 1 14 is a substituted or unsubstituted C 1 -C 30 Alkylene group; substituted or unsubstituted C 3 -C 30 Cycloalkylene group; substituted or unsubstituted C 3 -C 30 Heterocycloalkylene group; substituted or unsubstituted C 2 -C 30 Alkenylene group; substituted or unsubstituted C 3 -C 30 Cycloalkenylene group; substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene group; substituted or unsubstituted C 6 -C 30 arylene group; or substituted or unsubstituted C 1 -C 30 It is a heteroarylene group.

[0051] In one embodiment, L in Formula 1 14 is a deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, ester moiety, sulfonic acid ester moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20Alkoxy group, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 6 -C 20 aryl groups, or any combination thereof, substituted or unsubstituted, 1 -C 20 Alkylene group, C 3 -C 20 Cycloalkylene group, C 3 -C 20 Heterocycloalkylene group, C 2 -C 20 Alkenylene group, C 3 -C 20 Cycloalkenylene group, C 3 -C 20 Heterocycloalkenylene group, C 6 -C 20 Arylene groups, and C 1 -C 20 heteroarylene groups;

[0052] In one embodiment, L in Formula 1 14 Deuterium, halogens, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 C, substituted or unsubstituted with alkoxy, phenyl, naphthyl, or any combination thereof 1 -C 20 Alkylene group, C 3 -C 20 Cycloalkylene group, C 3 -C 20 heterocycloalkylene groups, phenylene groups, and naphthylene groups.

[0053] In Chemical Formula 1, a11 to a13 are each L 11 ~L 13 This means the number of iterations.

[0054] In one embodiment, a11 to a13 in Chemical Formula 1 each independently represent an integer of 1 to 3.

[0055] In one embodiment, a11 to a13 in Chemical Formula 1 are each independently 1.

[0056] In one embodiment, A in Formula 1 11 is a benzene group, a naphthalene group, a phenanthrene group, an anthracene group, a chrysene group, a pyrene group, a triphenylene group, a fluorene group, a pyrrole group, a pyridine group, a pyrimidine group, a pyrazine group, a triazine group, a quinoline group, an isoquinoline group, a carbazole group, a furan group, a benzofuran group, a dibenzofuran group, a thiophene group, a benzothiophene group, or a dibenzothiophene group.

[0057] In one embodiment, A in Formula 1 11 is a benzene group, a naphthalene group, a phenanthrene group, an anthracene group, a chrysene group, a pyrene group, a triphenylene group, or a fluorene group.

[0058] In one embodiment, A in Formula 1 11 is a benzene group or a naphthalene group.

[0059] In one embodiment, R in Formula 1 11 and R 12 are each independently hydrogen; deuterium; halogen; cyano group; hydroxy group; amino group; carboxylic acid group; thiol group; and deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, ester moiety, sulfonate ester moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 3 -C 20 Cycloalkyl groups, C 3 -C20 Cycloalkoxy group, C 6 -C 20 aryl groups, or any combination thereof, substituted or unsubstituted, 1 -C 20 Alkyl group, C 3 -C 20 Cycloalkyl groups and C 6 -C 20 aryl groups;

[0060] In one embodiment, R in Formula 1 11 is hydrogen, deuterium, halogen, CH 3 , C.H. 2 F, CHF 2 , C.F. 3 , C.H. 2 CH 3 , CHFCH 3 , CHFCH 2 F, CHFCHF 2 , CHFCF 3 , C.F. 2 CH 3 , C.F. 2 CH 2 F, C.F. 2 CHF 2 , or CF 2 CF 3 It is.

[0061] In one embodiment, R in Formula 1 12 is hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; C 1 -C 20 Alkyl group; C 1 -C 20 Halogenated alkyl group; C 3 -C 20 Cycloalkyl group; or C 6 -C 20 It is an aryl group.

[0062] In one embodiment, X in Formula 1 11 is OH.

[0063] In one embodiment, the first repeating unit may be represented by the following Formula 1-1:

[0064] [ka]

[0065] In Chemical Formula 1-1, L 11 ~L 14 , a11~a13, X 11 , R 11 and p are defined as in Chemical Formula 1. R 13 is hydrogen, deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, ester moiety, sulfonic acid ester moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, or C 6 -C 20 is an aryl group, b13 is an integer from 1 to 5; * indicates a bonding site with an adjacent atom.

[0066] In one embodiment, the first repeat unit may be selected from Group I: [ka]

[0067] In other embodiments, the polymer may further include at least one of a second repeat unit represented by Formula 2 and a third repeat unit represented by Formula 3: [ka] [ka]

[0068] In Chemical Formulas 2 and 3, L 21 ~L 23 and L 31 ~L 33 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or C which optionally contains a heteroatom. 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of a21 to a23 and a31 to a33 each independently represents an integer of 1 to 4, R 21 and R 31 are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which optionally contains a heteroatom. 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of X 21 is an acid labile group, X 31 is a non-acid labile group, * indicates a bonding site with an adjacent atom.

[0069] In one embodiment, L in Formulas 2 and 3 21 ~L 23 and L 31 ~L 33 are each independently 11 Please refer to the explanation related to.

[0070] In one embodiment, a21 to a23 and a31 to a33 in Chemical Formulae 2 and 3 each independently refer to the description of a11.

[0071] In one embodiment, R in Formulas 2 and 3 21 and R 31 are each independently R 11 Please refer to the explanation related to.

[0072] In one embodiment, X in Formula 2 21 can be represented by the following chemical formula 4-1 or 4-2: [ka]

[0073] In Chemical Formulas 4-1 and 4-2, X 41 is a carbon atom or a silicon atom, R 41 ~R 45 are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which optionally contains a heteroatom. 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of R 46 C, which may optionally contain heteroatoms 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of R 41 ~R 46 adjacent two of can be optionally joined to form a ring; * indicates a bonding site with an adjacent atom.

[0074] In one embodiment, R in formula 4-1 and 4-2 41 ~R 43is not simultaneously selected from hydrogen, deuterium, a halogen, a cyano group, and an amino group.

[0075] In one embodiment, X in Formula 2 21 may be selected from the following chemical formulas 5-1 to 5-11: [ka] [ka]

[0076] In chemical formulas 5-1 to 5-11, a51 is selected from integers of 0 to 6; R 51 and R 58 each independently represents a C which may optionally contain a heteroatom; 1 -C 20 is a linear, branched or cyclic monovalent hydrocarbon radical of R 52 ~R 57 are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which optionally contains a heteroatom. 1 -C 20 is a linear, branched or cyclic monovalent hydrocarbon radical of R 51 ~R 58 two adjacent groups may optionally be bonded to each other to form a ring; b54 is selected from integers from 1 to 10; * indicates a bonding site with an adjacent atom.

[0077] In the chemical formula 5-3, when a51 is 0, (CR 55 R 56 ) a51 is a single bond.

[0078] In particular, X in formula 2 21 may be selected from formulas 5-1 and 5-3.

[0079] In one embodiment, the second repeat unit may be represented by any one or more selected from the following Group II: [ka]

[0080] In one embodiment, X in Formula 3 31 is a hydrogen; a halogen; a cyano group; a hydroxy group; a carboxylic acid group; a thiol group; an amino group; or optionally contains one or more polar moieties selected from a halogen, a cyano group, a hydroxy group, a thiol group, a carboxylic acid group, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), a lactone moiety, a sultone moiety, and a carboxylic anhydride moiety. 1 -C 30 The alkyl group may be a linear, branched or cyclic monovalent hydrocarbon group.

[0081] In one embodiment, X in Formula 3 31 is a C group containing one or more polar moieties selected from hydrogen; a hydroxy group; O, C=O, C(=O)O, OC(=O), a lactone moiety, and a carboxylic anhydride moiety; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

[0082] In one embodiment, X in Formula 3 31 is a hydrogen atom; a hydroxyl group; or may be represented by any one of the following chemical formulas 6-1 to 6-10: [ka]

[0083] In chemical formulas 6-1 to 6-10, a61 is 1 or 2, R 61 ~R 66 are each independently a bond site to an adjacent atom; a hydrogen; a hydroxy group; a carboxylic acid group; an ester moiety; a carbonate moiety; a lactone moiety; a carboxylic anhydride moiety; or C 1 -C 20 is a linear, branched or cyclic monovalent hydrocarbon radical of R 61 ~R 63 One of them, R 64 One of these and R 65 and R 66 One of these is a bonding site with an adjacent atom, b61 is selected from integers of 1 to 4; b62 is selected from integers from 1 to 10; b63 is selected from integers from 1 to 8; b64 is selected from an integer from 1 to 5, b65 is selected from integers from 1 to 7; b66 is selected from integers from 1 to 11; b67 is selected from integers from 1 to 13; b68 is selected from integers from 1 to 15; m61 is selected from integers of 1 to 4.

[0084] In particular, X in formula 3 31 may be selected from a hydroxy group and formula 6-6.

[0085] In one embodiment, the third repeat unit may be represented by any one or more selected from the following Group III: [ka]

[0086] In one embodiment, the polymer comprises from 1 to 100 mol %, specifically from 5 to 100 mol %, and especially from 10 to 100 mol %, of the first repeat unit.

[0087] For example, the polymer can consist of a first repeating unit.

[0088] As another example, the polymer may include 0 to 99 mol %, specifically 1 to 99 mol %, and more specifically 10 to 90 mol %, of the second repeat unit.

[0089] As yet another example, the polymer can include 0 to 99 mol %, specifically 1 to 99 mol %, and more specifically 10 to 90 mol %, of the third repeat unit.

[0090] In one embodiment, the polymer can be composed of a first repeat unit and a second repeat unit, for example, the polymer can include 1-99 mol %, specifically 10-90 mol %, of the first repeat unit and 1-99 mol %, specifically 10-90 mol %, of the second repeat unit.

[0091] In one embodiment, the polymer may comprise a first repeat unit and a third repeat unit, for example, the polymer may comprise 1-99 mol %, specifically 10-90 mol %, of the first repeat unit, and 1-99 mol %, specifically 10-90 mol %, of the third repeat unit.

[0092] In one embodiment, the polymer may comprise a first repeat unit, a second repeat unit, and a third repeat unit, for example, the polymer may comprise 1-98 mol%, specifically 5-90 mol%, of the first repeat unit, 1-98 mol%, specifically 5-90 mol%, of the second repeat unit, and 1-98 mol%, specifically 5-90 mol%, of the third repeat unit.

[0093] The polymer may have a weight average molecular weight (Mw) of 1,000 to 500,000, specifically 3,000 to 100,000, and more specifically 5,000 to 50,000, measured by gel permeation chromatography using tetrahydrofuran solvent and polystyrene as the standard.

[0094] The polydispersity index (PDI: Mw / Mn) of the polymer may be 1.0 to 3.0, specifically 1.0 to 2.5. If the above range is satisfied, the possibility of foreign matter remaining on the pattern can be reduced, and deterioration of the pattern profile can be minimized. This makes the resist composition more suitable for forming fine patterns.

[0095] The structure (composition) of the polymer can be confirmed by FT-IR analysis, NMR analysis, X-ray fluorescence (XRF) analysis, mass spectrometry, UV analysis, single crystal X-ray structure analysis, powder X-ray diffraction (PXRD) analysis, liquid chromatography (LC) analysis, size exclusion chromatography (SEC) analysis, thermal analysis, etc. Detailed confirmation methods are as described in the Examples.

[0096] Generally, EUV (13.5 nm) has a lower number of photons than ArF (193 nm) immersion light source at the same exposure dose, so the lower the exposure dose, the more noticeable the noise in the boundary area between the area exposed by the EUV light source and the area not exposed to the EUV light source. In order to compensate for this, a higher content of photoacid generator must be used in the lithography process using the EUV light source compared to the lithography process using other light sources with the same light dose. However, if the resist composition contains a high content of photoacid generator, the glass transition temperature (Tg) of the base resin may change and the thermal stability may decrease. In addition, the resolution of the formed resist pattern may decrease due to the photoacid generator remaining during the lithography process using the EUV light source.

[0097] The polymer including the first repeating unit represented by Chemical Formula 1 can be crosslinked under an acid catalyst, specifically, by a thermal condensation reaction. That is, the polymer including the first repeating unit represented by Chemical Formula 1 can be crosslinked by, for example, a condensation reaction of X 11When is OH, crosslinking is formed by an etherification reaction. Therefore, even in the presence of a relatively small amount of photoacid generator, the physical properties of the polymer change, and the resolution of the resulting resist pattern can be improved.

[0098] In addition, the polymer including the first repeating unit represented by Chemical Formula 1 has reduced solubility in a developer due to the formation of crosslinks, compared to a polymer that is not crosslinked, and the resolution of the resist pattern obtained therefrom may be improved.

[0099] Furthermore, since the polymer including the first repeating unit represented by Chemical Formula 1 is crosslinked, the elastic modulus of the formed resist film can be improved, and defects due to pattern collapse during the pattern manufacturing process can be reduced.

[0100] Furthermore, since the polymer including the first repeating unit represented by Chemical Formula 1 is crosslinked, the etching resistance is improved, the etching rate is decreased, and the thickness of the resist film remaining after development is relatively thick, thereby improving the remaining film rate of the resist film.

[0101] [Resist composition] According to another aspect, there is provided a resist composition comprising the aforementioned polymer, a photoacid generator and an organic solvent. The resist composition can have properties such as improved developability and / or improved resolution.

[0102] The resist composition changes in solubility in a developer by exposure to high-energy radiation. The resist composition may be a positive resist composition in which an exposed portion of the resist film is dissolved and removed to form a positive resist pattern, or a negative resist composition in which an unexposed portion of the resist film is dissolved and removed to form a negative resist pattern. Specifically, the resist composition is a negative composition.

[0103] Furthermore, the resist composition according to one embodiment may be for an alkaline development process that utilizes an alkaline developer in the development treatment during resist pattern formation, or may be for a solvent development process that utilizes a developer containing an organic solvent (hereinafter also referred to as an organic developer) in the development treatment.

[0104] The polymer containing the repeating unit represented by Chemical Formula 1 used in the resist composition may be one type, or two or more different types may be used in combination.

[0105] The polymer can be used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the resist composition. Specifically, the polymer is used in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the resist composition. If the above range is satisfied, any performance loss, such as a decrease in sensitivity and / or formation of foreign particles due to insufficient solubility, can be reduced.

[0106] The polymer is as described above, and the following describes the photoacid generator, the organic solvent, and optional components such as a quencher that may be contained as necessary.

[0107] <Photoacid generator> The photoacid generator may be any compound that generates an acid upon exposure to high energy radiation, such as UV, DUV, EB, EUV, X-rays, alpha rays, gamma rays, and the like.

[0108] Photoacid generators may include sulfonium salts, iodonium salts, and combinations thereof.

[0109] In one embodiment, the photoacid generator is represented by Formula 7: [Chemical formula 7] B 71 + A 71 - In Chemical Formula 7, B 71 + is represented by the following chemical formula 7A, 71 -is represented by any one of the following chemical formulas 7B to 7D, B 71 + and A 71 - is optionally linked through a carbon-carbon covalent bond; [ka]

[0110] In Chemical Formulae 7A to 7D, L 71 ~L 73 are each independently a single bond or CRR', R and R' are each independently hydrogen, deuterium, a halogen, a cyano group, a hydroxyl group, or C 1 -C 30 Alkyl group, C 1 -C 30 Halogenated alkyl groups, C 1 -C 30 Alkoxy group, C 3 -C 30 Cycloalkyl group, or C 3 -C 30 is a cycloalkoxy group, n71 to n73 each independently represent 1, 2, or 3; x71 and x72 each independently represent 0 or 1; R 71 ~R 73 each independently represents a C which may optionally contain a heteroatom; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of R 71 ~R 73 adjacent two of the groups may be optionally linked to each other to form a fused ring; R 74 ~R 76 are each independently hydrogen; halogen; or C which may optionally contain heteroatoms. 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

[0111] For example, in formula 7, B 71 + is represented by chemical formula 7A, and A 71 - is represented by Chemical Formula 7B. Specifically, R 71 ~R 73 are each a phenyl group.

[0112] The photoacid generator is included in an amount of 0.01 to 40 parts by weight, 0.1 to 40 parts by weight, or 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer. If the above range is satisfied, appropriate resolution can be achieved and problems associated with foreign particles after development or during stripping can be reduced.

[0113] The photoacid generator may be used alone or in combination of two or more different types.

[0114] <Organic solvent> There are no particular limitations on the organic solvent contained in the resist composition, so long as it is capable of dissolving or dispersing the polymer, photoacid generator, and optional components that are contained as necessary, such as a quencher.

[0115] The organic solvent may be used alone or in combination of two or more different organic solvents. A mixed solvent of water and an organic solvent may also be used.

[0116] Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, and hydrocarbon-based solvents.

[0117] More specifically, examples of the alcohol-based solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, 4-methyl-2-pentanol (MIBC), sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, and the like. monoalcohol solvents such as ethanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;Examples of the polyhydric alcohol-containing ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

[0118] Examples of the ether solvent include dialkyl ether solvents such as diethyl ether, dipropyl ether, and dibutyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole.

[0119] Examples of ketone solvents include chain ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; 2,4-pentanedione, acetonylacetone, and acetophenone.

[0120] Examples of the amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methyl-2-pyrrolidone; and chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.

[0121] Examples of ester-based solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate (n-BA), isobutyl acetate, sec-butyl acetate, t-butyl acetate, n-pentyl acetate, isopentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexane, hexanediaminetetraacetate ... Acetate ester solvents such as hexyl acetate, methylcyclohexyl acetate, and n-nonyl acetate; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol Examples of the polyhydric alcohol-containing ether carboxylate solvents include propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone and δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; lactate ester solvents such as methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate; glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

[0122] Examples of sulfoxide solvents include dimethyl sulfoxide and diethyl sulfoxide.

[0123] Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-amylnaphthalene.

[0124] Specifically, the organic solvent is selected from alcohol solvents, amide solvents, ester solvents, sulfoxide solvents, and any combination thereof. More specifically, the solvent is selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, ethyl lactate, dimethyl sulfoxide, and any combination thereof.

[0125] On the other hand, when an acetal form of an acid labile group is used, the organic solvent may further contain a high boiling alcohol, such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, or 1,3-butanediol, to accelerate the deprotection reaction of the acetal.

[0126] The organic solvent can be used in an amount of 200 to 20,000 parts by weight, specifically 2,000 to 10,000 parts by weight, based on 100 parts by weight of the polymer.

[0127] <Quencher> The resist composition may further include a quencher.

[0128] The quencher may be a salt that generates an acid that is less acidic than the acid generated by the photoacid generator.

[0129] Quenchers may include ammonium salts, sulfonium salts, iodonium salts, and combinations thereof.

[0130] In one embodiment, the quencher is represented by Formula 8: [Chemical formula 8] B 81 + A 81 - In Chemical Formula 8, B 81 + is represented by any one of the following chemical formulas 8A to 8C, 81 - is represented by any one of the following chemical formulas 8D to 8F, B 81 + and A 81 - is optionally linked through a carbon-carbon covalent bond; [ka]

[0131] In Chemical Formulae 8A to 8F, L 81 and L 82 are each independently a single bond or CRR', R and R' are each independently hydrogen, deuterium, a halogen, a cyano group, a hydroxyl group, or C 1 -C 30 Alkyl group, C 1 -C 30 Halogenated alkyl groups, C 1 -C 30 Alkoxy group, C 3 -C 30 Cycloalkyl group, or C 3 -C 30 is a cycloalkoxy group, n81 and n82 are each independently 1, 2 or 3; x81 is either 0 or 1, R 81 ~R 84each independently represents a C which may optionally contain a heteroatom; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of R 81 ~R 84 adjacent two of the groups may be optionally linked to each other to form a fused ring; R 85 and R 86 is hydrogen; halogen; or C, which may optionally contain heteroatoms. 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

[0132] The quencher is included in an amount of 0 to 10 parts by weight, 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight, based on 100 parts by weight of the polymer. If the above range is satisfied, appropriate resolution can be achieved and problems associated with foreign particles after development or during stripping can be reduced.

[0133] The quencher may be used alone or in combination of two or more different types.

[0134] <Base resin> The resist composition may further contain a base resin.

[0135] The base resin may include repeat units containing acid labile groups, as represented by Formula 2: [ka]

[0136] In Chemical Formula 2, L 21 ~L 23 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or C which optionally contains a heteroatom. 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of a21 to a23 each independently represents an integer of 1 to 4, R 21 is a C group which may optionally contain hydrogen, deuterium, a halogen, a cyano group, a hydroxy group, an amino group, a carboxylic acid group, a thiol group, an ester moiety, a sulfonate ester moiety, a carbonate moiety, a lactone moiety, a sultone moiety, a carboxylic anhydride moiety, or a heteroatom. 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of X 21 is an acid labile group, * indicates a bonding site with an adjacent atom.

[0137] For an explanation of Chemical Formula 2, see above.

[0138] The base resin containing the repeating unit represented by Chemical Formula 2 is decomposed under the action of an acid to generate a carboxyl group, thereby being switched to alkali-solubility.

[0139] In addition to the repeating unit represented by Chemical Formula 2, the base resin may further include a repeating unit represented by Chemical Formula 3 below: [ka]

[0140] In Chemical Formula 3, L 31 ~L 33 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or C which optionally contains a heteroatom. 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of a31 to a33 each independently represents an integer of 1 to 4, R 31is a C group which may optionally contain hydrogen, deuterium, a halogen, a cyano group, a hydroxy group, an amino group, a carboxylic acid group, a thiol group, an ester moiety, a sulfonate ester moiety, a carbonate moiety, a lactone moiety, a sultone moiety, a carboxylic anhydride moiety, or a heteroatom. 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of X 31 is a non-acid labile group, * indicates a bonding site with an adjacent atom.

[0141] For an explanation of Chemical Formula 3, see above.

[0142] For example, in the ArF lithography process, X 31 contains a lactone ring as a polar moiety, and in KrF, EB and EUV lithography processes, X 31 may be phenol.

[0143] In one embodiment, the base resin may further include moieties that include anions and / or cations, for example, the base resin may further include moieties that are derivatized to include photoacid generators and / or quenchers attached to the side chains.

[0144] The base resin may have a weight average molecular weight (Mw) of 1,000 to 500,000, specifically 3,000 to 100,000, as measured by gel permeation chromatography using tetrahydrofuran solvent and polystyrene as the standard.

[0145] The polydispersity index (PDI: Mw / Mn) of the base resin may be 1.0 to 3.0, specifically 1.0 to 2.0. If the above range is satisfied, the possibility of foreign matter remaining on the pattern can be reduced, and deterioration of the pattern profile can be minimized. This makes the resist composition more suitable for forming fine patterns.

[0146] The base resin can be produced by any appropriate method, for example, by dissolving an unsaturated bond-containing monomer in an organic solvent and then thermally polymerizing the monomer in the presence of a radical initiator.

[0147] In the base resin, the mole fraction (mol %) of each repeating unit derived from each monomer is as follows, but is not limited to: i) containing 1 to 60 mol %, specifically 5 to 50 mol %, more specifically 10 to 50 mol %, of a repeating unit represented by Chemical Formula 2; ii) Contains 40 to 99 mol %, specifically 50 to 95 mol %, and more specifically 50 to 90 mol %, of the repeating unit represented by Chemical Formula 3.

[0148] The base resin may be a single polymer or may comprise a mixture of two or more polymers differing from one another in composition, weight average molecular weight and / or polydispersity index.

[0149] <Optional ingredients> The resist composition may further include a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof, as required.

[0150] The resist composition may further contain a surfactant to improve coating properties, developability, etc. Specific examples of the surfactant include nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. The surfactant may be a commercially available product or a synthetic product. Examples of commercially available surfactants include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75 and POLYFLOW No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP EF301, FTOP EF303 and FTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE (registered trademark) F171, MEGAFACE F173, R40, R41 and R43 (manufactured by DIC Corporation), Fluorad (registered trademark) FC430 and Fluorad FC431 (manufactured by 3M), AsahiGuard AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105 and Surflon Examples include SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.).

[0151] The surfactant may be contained in an amount of 0 to 20 parts by weight based on 100 parts by weight of the polymer.

[0152] The surfactant may be used alone or in combination of two or more different surfactants.

[0153] The method for producing the resist composition is not particularly limited, and for example, a method of mixing a polymer, a photoacid generator, and an optional component added as needed in an organic solvent can be used. The temperature and time during mixing are not particularly limited. If necessary, filtration can be performed after mixing.

[0154] [Pattern formation method] Hereinafter, a pattern forming method according to an exemplary embodiment will be described in more detail with reference to Fig. 1 and Fig. 2A to Fig. 2C. Fig. 1 is a flow chart showing a pattern forming method according to an exemplary embodiment, and Fig. 2A to Fig. 2C are side cross-sectional views showing a pattern forming method according to an exemplary embodiment. Hereinafter, a pattern forming method using a negative resist composition will be specifically described as an example, but is not limited thereto.

[0155] 1, the method for forming a pattern includes a step of forming a resist film by applying a resist composition (S101), a step of exposing at least a part of the resist film to high energy radiation (S102), and a step of developing the exposed resist film using a developer (S103). The steps may be omitted or may be performed in a different order, if necessary.

[0156] First, a substrate 100 is prepared. The substrate 100 can be, for example, a semiconductor substrate such as a silicon substrate or a germanium substrate, glass, quartz, ceramic, copper, etc. In some embodiments, the substrate 100 can include a III-V compound such as GaP, GaAs, or GaSb.

[0157] A resist composition can be applied to a substrate 100 to a desired thickness, specifically by a coating method, to form a resist film 110. If necessary, the resist film 110 can be heated (called pre-bake (PB) or post-annealing bake (PAB)) to remove any organic solvent remaining therein.

[0158] The coating method may be spin coating, dipping, roller coating, or other common coating methods. Among them, spin coating may be used in particular, and the viscosity, concentration, and / or spin speed of the resist composition may be adjusted to form a resist film 110 of a desired thickness. Specifically, the thickness of the resist film 110 may be 10 nm to 300 nm. More specifically, the thickness of the resist film 110 may be 30 nm to 200 nm.

[0159] The lower limit of the pre-baking temperature may be 60° C. or more, specifically 80° C. or more. The upper limit of the pre-baking temperature may be 150° C. or less, specifically 140° C. or less. The lower limit of the pre-baking time may be 5 seconds or more, specifically 10 seconds or more. The upper limit of the pre-baking time may be 600 seconds or less, specifically 300 seconds or less.

[0160] Before applying the resist composition to the substrate 100, a layer to be etched (not shown) may be further formed on the substrate 100. The layer to be etched refers to a layer to which an image from a resist pattern is transferred and converted into a predetermined pattern. In one embodiment, the layer to be etched may be formed to include an insulating material such as silicon oxide, silicon nitride, or silicon oxynitride. In some embodiments, the layer to be etched may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, or a metal silicide nitride. In some embodiments, the layer to be etched may be formed to include a semiconductor material such as polysilicon.

[0161] In one embodiment, in order to maximize the efficiency of the resist, an anti-reflective coating may be further formed on the substrate 100. The anti-reflective coating may be an organic or inorganic anti-reflective coating.

[0162] In one embodiment, in order to reduce the influence of alkaline impurities and the like contained in the process, a protective film can be further provided on the resist film 100. Furthermore, when performing immersion exposure, in order to prevent direct contact between the immersion medium and the resist film 100, for example, a protective film for immersion can be provided on the resist film 100.

[0163] Next, at least a portion of the resist film 110 can be exposed to high-energy rays. For example, high-energy rays that have passed through a mask 120 are irradiated onto at least a portion of the resist film 110. As a result, the resist film 110 can have an exposed portion 111 and a non-exposed portion 112.

[0164] The exposure is performed by irradiating a high-energy beam through a mask having a predetermined pattern, and in some cases using a liquid such as water as a medium. Examples of high-energy beams include electromagnetic waves such as ultraviolet, far ultraviolet, extreme ultraviolet (EUV, wavelength 13.5 nm), X-rays, and gamma rays; and charged particle beams such as electron beams (EB) and alpha rays. Irradiation with these high-energy beams is collectively called "exposure".

[0165] The exposure light source is a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or a F 2 A variety of lasers can be used, including those that emit laser light in the ultraviolet region such as an excimer laser (wavelength 157 nm), those that convert the wavelength of laser light from a solid-state laser light source (such as a YAG or semiconductor laser) and emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, and those that irradiate electron beams or extreme ultraviolet (EUV). During exposure, exposure is usually performed through a mask that corresponds to the desired pattern, but if the exposure light source is an electron beam, exposure can also be performed by direct writing without using a mask.

[0166] The cumulative dose of high-energy rays is, for example, 2000 mJ / cm when using extreme ultraviolet rays as high-energy rays. 2 Specifically, 500 mJ / cm 2In addition, when an electron beam is used as the high energy beam, the cumulative dose is 5000 μC / cm 2 Specifically, 1000μC / cm 2 It may be the following.

[0167] In addition, a post-exposure bake (PEB) can be performed after the exposure. The lower limit of the PEB temperature may be 50° C. or more, specifically 80° C. or more. The upper limit of the PEB temperature may be 180° C. or less, specifically 130° C. or less. The lower limit of the PEB time may be 5 seconds or more, specifically 10 seconds or more. The upper limit of the PEB time may be 600 seconds or less, specifically 300 seconds or less.

[0168] Without being limited to a particular theory, crosslinks may be formed in the polymer during PEB by a condensation reaction catalyzed by the acid formed by exposure to light.

[0169] A developer can then be used to develop the exposed resist film 110. The exposed areas 111 will remain and will not be washed away by the developer, while the unexposed areas 112 will be washed away by the developer.

[0170] Examples of the developer include an alkaline developer and a developer containing an organic solvent (hereinafter, also referred to as an "organic developer"). Examples of the development method include a dipping method, a paddle method, a spray method, and a dynamic administration method. The development temperature may be, for example, 5° C. or higher and 60° C. or lower, and the development time may be, for example, 5 seconds or higher and 300 seconds or lower.

[0171] Examples of the alkaline developer include an alkaline aqueous solution in which one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN) are dissolved. The alkaline developer may further contain a surfactant.

[0172] The lower limit of the content of the alkaline compound in the alkaline developer may be 0.1% by mass or more, specifically 0.5% by mass or more, more specifically 1% by mass or more, and the upper limit of the content of the alkaline compound in the alkaline developer may be 20% by mass or less, specifically 10% by mass or less, more specifically 5% by mass or less.

[0173] As the organic solvent contained in the organic developer, for example, the same organic solvents as those exemplified in the <Organic solvent> section of [Resist composition] can be used.

[0174] The lower limit of the content of the organic solvent in the organic developer may be 80% by mass or more, specifically 90% by mass or more, more specifically 95% by mass or more, and particularly 99% by mass or more.

[0175] The organic developer may contain a surfactant, a trace amount of water, and / or acetic acid (AA). During development, the development can be stopped by replacing the organic developer with a different type of solvent.

[0176] The resist pattern after development can be further washed. As the washing liquid, ultrapure water, a rinse liquid, etc. can be used. As the rinse liquid, there is no particular limitation as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. For example, the rinse liquid may be an alcohol-based solvent or an ester-based solvent. After washing, the rinse liquid remaining on the substrate and the pattern can be removed. In addition, when ultrapure water is used, the water remaining on the substrate and the pattern can be removed.

[0177] The developer may be used alone or in combination of two or more kinds.

[0178] After forming the resist pattern as described above, the resist pattern is etched to obtain a patterned wiring board. The etching method is carried out by a known method such as dry etching using plasma gas, or wet etching using an alkaline solution, a cupric chloride solution, a ferric chloride solution, or the like.

[0179] After forming the resist pattern, plating can be carried out. The plating method is not particularly limited, but examples thereof include copper plating, solder plating, nickel plating, and gold plating.

[0180] The remaining resist pattern after etching can be peeled off with an organic solvent. Examples of such organic solvents include, but are not limited to, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), etc. The peeling method includes, but is not limited to, a dipping method, a spray method, etc. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board, and may have a small diameter through hole.

[0181] In one embodiment, the wiring board can also be formed by a method in which a resist pattern is formed, a metal is evaporated in a vacuum, and then the resist pattern is dissolved in a solution, that is, a lift-off method.

[0182] 4A-4E are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention.

[0183] 4A, before forming the resist film 110 on the substrate 100, a material layer 130 may be formed on the substrate 100. The resist film 110 may be formed on the upper side of the material layer 130. The material layer 130 may include an insulating material (e.g., silicon oxide, silicon nitride), a semiconductor material (e.g., silicon), or a metal (e.g., copper). In some embodiments, the material layer 130 may have a multi-layer structure. The material of the material layer 130 is different from the material of the substrate 100.

[0184] As shown in FIG. 4B, the resist film 110 undergoes a pre-exposure bake process and is exposed to high energy rays through a mask 120, after which the resist film 110 includes an exposed region 111 and a non-exposed region 112.

[0185] 4C, the exposed resist film 110 is developed using a developer (e.g., a developer). The exposed portion 111 is washed away by the developer, and the non-exposed portion 112 is not washed away by the developer and remains.

[0186] As shown in FIG. 4D, the exposed portions of the material layer 130 may be etched using the resist pattern 110 as a mask to form a material pattern 135 on the substrate 100. As shown in FIG.

[0187] As shown in FIG. 4E, the resist pattern 110 may be removed.

[0188] 5A-5E are cross-sectional side views illustrating a method of forming a semiconductor device according to one embodiment.

[0189] 5A, a gate dielectric 505 (e.g., silicon oxide) is formed on a substrate 500. The substrate 500 may be a semiconductor substrate, such as a silicon substrate. A gate layer 515 (e.g., doped polysilicon) is formed on the gate dielectric 505. A hard mask layer 520 is formed on the gate layer 515.

[0190] 5B, a resist pattern 540b may be formed on the hard mask layer 520. The resist pattern 540b may be formed using a resist composition according to an embodiment of the present invention. The resist composition may include an organic solvent.

[0191] As shown in FIG. 5C, the gate layer 515 and the gate dielectric 505 may be etched to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a.

[0192] As shown in FIG. 5D, a spacer layer may be formed on the gate electrode pattern 515a and the gate dielectric pattern 505a. The spacer layer may be formed using a deposition process (e.g., CVD). The spacer layer may be etched to form spacers 535a (e.g., silicon nitride) on the sidewalls of the gate electrode pattern 515a and the gate dielectric pattern 505a. After the spacers 535a are formed, ions may be implanted into the substrate 500 to form source / drain impurity regions S / D.

[0193] 5E, an interlayer insulating film 560 (e.g., oxide) may be formed on the substrate 500 to cover the gate electrode pattern 515a, the gate dielectric pattern 505a, and the spacer 535a. Then, electrical contacts 570a, 570b, and 570c connected to the gate electrode 515a and the S / D regions are formed in the interlayer insulating film 560. The electrical contacts 570a, 570b, and 570c are formed of a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewalls of the interlayer insulating film 560 and the electrical contacts 570a, 570b, and 570c.

[0194] 5A to 5E show an example of forming a transistor, but the present invention is not limited thereto.

[0195] The resist composition according to one or more embodiments can be used in patterning processes to form other types of semiconductor devices. The resist composition may include an organic solvent.

[0196] The present invention will be described in more detail using the following examples and comparative examples, but the technical scope of the present invention is not limited to only the following examples.

[0197] [Example] Synthesis Example 1: Synthesis of Polymer A [ka]

[0198] 4g (22.7mmol) of 4-vinylbenzyl acetate (VBA, Monomer 1) and 0.5g (2.3mmol) of azo initiator (V601) were dissolved in methyl ethyl ketone (MEK) at 35wt% and reacted at 70°C for 4 hours. Then, precipitation was performed using hexane and the mixture was dried to obtain a solid. The obtained solid was dispersed in methanol and added with NaOCH 3 A solution (25 wt%, methanol) was added to the obtained solid in a molar ratio of 2 times, and the reaction was carried out at room temperature for 4 hours to obtain a reaction product. Then, the reaction product was added with 50 mL of deionized water (DW) and acetic acid (added NaOCH 3 (2 times molar ratio to the above) was added, and the mixture was extracted with ethyl acetate (EA), followed by precipitation using hexane. The resulting precipitate was dried at 40° C. for 24 hours to obtain polymer A as a white powder.

[0199] Synthesis Examples 2-8 The same method as in Synthesis Example 1 was used, except that Monomers 1 to 3 in Table 1 below were used instead of Monomer 1. For the polymers obtained in Synthesis Examples 1 to 8, 1H-NMR, weight average molecular weight and PDI were measured and are shown in Table 2 below.

[0200] [Table 1] [ka]

[0201] [Table 2]

[0202] Evaluation example 1: Thin film development evaluation (1) Terminology E 0 is the exposure dose at which the thin film begins to harden, and E 1 means the exposure dose at the saturation point where the film thickness does not increase any more. The remaining film ratio is the film thickness at the saturation point divided by the initial thickness, expressed as a percentage, and γ is the contrast curve, which is calculated by the following Equation 1.

[0203]

number

[0204] NRT is an abbreviation for normalized remaining thickness.

[0205] (2) Thin film development evaluation The polymers, PAG A, and PDQ A shown in Table 3 were dissolved in a propylene glycol methyl ether / propylene glycol methyl ether acetate (PGME / PGMEA) 7 / 3 (wt / wt) solution so that the total amount was 1.5 wt %. The weight ratios of the polymers, PAG A, and PDQ A are as shown in Table 3 below. The casting solution was spin-coated at 1500 rpm on a silicon wafer coated with a 3 nm HMDS underlayer, and then dried at 130°C for 1 minute to prepare a 50 nm thick film. Next, DUV with a wavelength of 248 nm was applied at 0-50 mJ / cm. 2 After exposure at a dose of 100 nm, post-exposure baking at 110° C. for 60 seconds and immersion at 25° C. for 20 seconds in the developer shown in Table 3 below, the remaining film thickness was measured using a 3D optical profiler (Bruker, Contour X-100) and shown in Table 3 and Figures 3A to 3J below. Figure 3A is a graph showing the data for Example 1-1, Figure 3B is a graph showing the data for Example 1-2, Figure 3C is a graph showing the data for Example 1-3, Figure 3D is a graph showing the data for Example 1-4, Figure 3E is a graph showing the data for Example 1-5, Figure 3F is a graph showing the data for Example 1-6, Figure 3G is a graph showing the data for Example 1-7, Figure 3H is a graph showing the data for Example 1-8, Figure 3I is a graph showing the data for Comparative Example 1-1, and Figure 3J is a graph showing the data for Comparative Example 1-2.

[0206] [Table 3] [ka]

[0207] Referring to Table 3, Examples 1-1 to 1-8 have smaller E 1 It can be seen that the γ value is larger than that of the comparative example 1-2, suggesting that Examples 1-1 to 1-8 have improved sensitivity compared to the comparative example 1-2.

[0208] In addition, it can be seen that Examples 1-2 to 1-5 have a larger γ value than Example 1-1, and Examples 1-6 to 1-8 have a smaller E value than Example 1-1. 0It was confirmed that the value was shown.

[0209] Evaluation example 2: Elastic modulus evaluation results Silicon wafers coated with the polymers shown in Table 4 below were cut to a size of 10 mm x 10 mm to prepare test specimens. The elastic modulus of the thin films was measured in tapping mode with a tip radius of 30 nm and a spring constant of 40 N / m using a Bruker Dimension Icon XR instrument and a RTESPA-300-30 probe. The results are shown in Table 4 below.

[0210] [Table 4]

[0211] It was confirmed that the elastic modulus of Examples 2-1 to 2-8 was improved by about 16% to 57% and specifically improved by up to 57% compared to the elastic modulus of Comparative Example 2-1. Without being limited to a specific theory, it is expected that the elastic modulus of Polymers A, B-1 to B-4, and C-1 to C-3 is improved compared to Polymer D, which is not crosslinked, because the polymers are crosslinked.

[0212] Evaluation example 3: Etching resistance evaluation Using a dry etching system Plasmalab 100 RIE (obtained from Oxford Instruments Plasma Technology), CF 4 Gas flow rate: O 2 The etching rates were measured from the change in thickness after etching for 10 seconds, 20 seconds, and 30 seconds using an etching gas with a gas flow rate of 20:5 (sccm), and are shown in Table 5 below.

[0213] [Table 5]

[0214] It was confirmed that the etching rates of Examples 3-1 to 3-8 were reduced by about 9% to 31% compared to the etching rate of Comparative Example 3-1, specifically by up to 31%. Without being limited to a particular theory, it is expected that the etching rates of Polymers A, B-1 to B-4, and C-1 to C-3 are slower than that of Polymer D, which is not crosslinked, because the polymers are crosslinked. [Explanation of symbols]

[0215] S101: Coating a resist composition to form a resist film S102 Exposing at least a portion of the resist film to high energy radiation. S103: Developing the exposed resist film using a developer. 100 Substrates 110 Resist film 111 Exposure section 112 Non-exposed area 120 Mask 130 Material layer 135 Material Patterns 500 boards 505 Gate Dielectric 505a Gate dielectric pattern 515 Gate Layer 515a Gate electrode pattern, gate electrode 520 Hard Mask Layer 520a hard mask pattern 535a Spacer 540b Resist pattern 560 Interlayer insulating film 570a Electrical contact 570b Electrical contact 570c ​​Electrical Contact

Claims

1. A polymer comprising a first repeating unit represented by the following formula 1: 【Chemistry 1】 In the above Chemical Formula 1, L １１ ~L １３ are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or C(=O) optionally containing a heteroatom. １ -C ３０ is a linear, branched or cyclic divalent hydrocarbon radical of L １４ is C, which may optionally contain heteroatoms; １ -C ３０ is a linear, branched or cyclic divalent hydrocarbon radical of a11 to a13 each independently represent an integer of 1 to 4; A １１ is C ６ -C ３０ Aromatic group or C １ -C ３０ is a heteroaromatic group, R １１ and R １２ are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of b12 is selected from integers from 1 to 10; X １１ is OH, SH or NH ２ and p is selected from an integer from 1 to 5; * indicates a bonding site with an adjacent atom.

2. L １１ ~L １３ are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); １ -C ３０ Alkylene group; substituted or unsubstituted C ３ -C ３０ Cycloalkylene group; substituted or unsubstituted C ３ -C ３０ Heterocycloalkylene group; substituted or unsubstituted C ２ -C ３０ Alkenylene group; substituted or unsubstituted C ３ -C ３０ Cycloalkenylene group; substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylene group; substituted or unsubstituted C ６ -C ３０ an arylene group; or a substituted or unsubstituted C １ -C ３０ is a heteroarylene group, L １４ is a substituted or unsubstituted C １ -C ３０ Alkylene group; substituted or unsubstituted C ３ -C ３０ Cycloalkylene group; substituted or unsubstituted C ３ -C ３０ Heterocycloalkylene group; substituted or unsubstituted C ２ -C ３０ Alkenylene group; substituted or unsubstituted C ３ -C ３０ Cycloalkenylene group; substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylene group; substituted or unsubstituted C ６ -C ３０ an arylene group; or a substituted or unsubstituted C １ -C ３０ The polymer of claim 1 which is a heteroarylene group.

3. A １１ is a benzene group, a naphthalene group, a phenanthrene group, an anthracene group, a chrysene group, a pyrene group, a triphenylene group, a fluorene group, a pyrrole group, a pyridine group, a pyrimidine group, a pyrazine group, a triazine group, a quinoline group, an isoquinoline group, a carbazole group, a furan group, a benzofuran group, a dibenzofuran group, a thiophene group, a benzothiophene group, or a dibenzothiophene group.

4. X １１ The polymer of claim 1 , wherein is OH.

5. The polymer of claim 1, wherein the first repeating unit is represented by the following formula 1-1: 【Chemistry 2】 In the above Chemical Formula 1-1, L １１ ~L １４ , a11-a13, X １１ , R １１ and p are defined as in Formula 1 above. R １３ is hydrogen, deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, ester moiety, sulfonic acid ester moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C １ -C ２０ Alkoxy group, C ３ -C ２０ Cycloalkyl group, C ３ -C ２０ Cycloalkoxy group, or C ６ -C ２０ is an aryl group, b13 is an integer from 1 to 5, * indicates a bonding site with an adjacent atom.

6. 2. The polymer of claim 1, wherein the first repeat unit is selected from Group I: 【Chemistry 3】 。

7. The polymer of claim 1, further comprising at least one of a second repeating unit represented by the following formula 2 and a third repeating unit represented by the following formula 3: 【Chemistry 4】 In the above Chemical Formulas 2 and 3, L ２１ ~L ２３ and L ３１ ~L ３３ are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or C(=O) optionally containing a heteroatom. １ -C ３０ is a linear, branched or cyclic divalent hydrocarbon radical of a21 to a23 and a31 to a33 each independently represent an integer of 1 to 4, R ２１ and R ３１ are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of X ２１ is an acid labile group, X ３１ is a non-acid labile group, * indicates a bonding site with an adjacent atom.

8. X ２１ The polymer according to claim 7, represented by the following chemical formula 4-1 or 4-2: 【Chemistry 5】 In the above chemical formulas 4-1 and 4-2, X ４１ is a carbon atom or a silicon atom, R ４１ ~R ４５ are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of R ４６ is C, which may optionally contain heteroatoms; １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of R ４１ ~R ４６ adjacent two of may optionally be joined to each other to form a ring; * indicates a bonding site with an adjacent atom.

9. X ２１ is selected from the following chemical formulas 5-1 to 5-11: 【Chemistry 6】 In the above Chemical Formulas 5-1 to 5-11, a51 is selected from integers of 0 to 6; R ５１ and R ５８ each independently represents a C which may optionally contain a heteroatom; １ -C ２０ is a linear, branched or cyclic monovalent hydrocarbon radical of R ５２ ~R ５７ are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C which may optionally contain a heteroatom. １ -C ２０ is a linear, branched or cyclic monovalent hydrocarbon radical of R ５１ ~R ５８ two adjacent groups may optionally be bonded to each other to form a ring; b54 is selected from integers from 1 to 10; * indicates a bonding site with an adjacent atom.

10. The polymer of claim 7 , wherein the second repeat unit is represented by any one or more selected from the following Group II: 【Chemistry 7】 。

11. X ３１ is a hydrogen; a halogen; a cyano group; a hydroxy group; a carboxylic acid group; a thiol group; an amino group; or C which optionally contains one or more polar moieties selected from a halogen, a cyano group, a hydroxy group, a thiol group, a carboxylic acid group, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), a lactone moiety, a sultone moiety, and a carboxylic anhydride moiety. １ -C ３０ 8. The polymer of claim 7, wherein the R is a linear, branched or cyclic monovalent hydrocarbon group of the formula:

12. X ３１ is hydrogen; a hydroxyl group; or any one of the following chemical formulas 6-1 to 6-10: 【Chemistry 8】 In the above Chemical Formulas 6-1 to 6-10, a61 is 1 or 2; R ６１ ~R ６６ are each independently a bond site to an adjacent atom; a hydrogen atom; a hydroxy group; a carboxylic acid group; an ester moiety; a carbonate moiety; a lactone moiety; a carboxylic anhydride moiety; or C １ -C ２０ is a linear, branched or cyclic monovalent hydrocarbon radical of R ６１ ~R ６３ One of them, R ６４ One of the following, and R ６５ and R ６６ One of these is a bonding site with an adjacent atom, b61 is selected from integers of 1 to 4; b62 is selected from integers from 1 to 10; b63 is selected from integers from 1 to 8; b64 is selected from integers from 1 to 5; b65 is selected from integers from 1 to 7; b66 is selected from integers from 1 to 11; b67 is selected from integers from 1 to 13; b68 is selected from integers from 1 to 15; m61 is selected from integers of 1 to 4.

13. The polymer of claim 9 , wherein the third repeat unit is represented by any one or more selected from the following Group III: 【Chemistry 9】 。

14. A resist composition comprising the polymer according to claim 1 , a photoacid generator, and an organic solvent.

15. The resist composition according to claim 14, wherein the photoacid generator is represented by the following chemical formula 7: [Chemical formula 7] B ７１ ＋ A ７１ － In the above Chemical Formula 7, B ７１ ＋ is represented by the following chemical formula 7A, ７１ － is represented by any one of the following chemical formulas 7B to 7D, B ７１ ＋ and A ７１ － is optionally linked through a carbon-carbon covalent bond; 【Chemistry 10】 In the above Chemical Formulas 7A to 7D, L ７１ ~L ７３ each independently represents a single bond or CRR′; R and R′ are each independently hydrogen, deuterium, a halogen, a cyano group, a hydroxyl group, C １ -C ３０ Alkyl group, C １ -C ３０ Halogenated alkyl group, C １ -C ３０ Alkoxy group, C ３ -C ３０ Cycloalkyl group, or C ３ -C ３０ is a cycloalkoxy group, n71 to n73 each independently represent 1, 2, or 3; x71 and x72 each independently represent 0 or 1; R ７１ ~R ７３ each independently represents a C which may optionally contain a heteroatom; １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of R ７１ ~R ７３ adjacent two of may optionally be bonded to each other to form a fused ring; R ７４ ~R ７６ are each independently hydrogen; halogen; or C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

16. The resist composition of claim 14 further comprising a quencher.

17. The resist composition according to claim 16, wherein the quencher is represented by the following chemical formula 8: [Chemical formula 8] B ８１ ＋ A ８１ － In the above Chemical Formula 8, B ８１ ＋ is represented by any one of the following chemical formulas 8A to 8C, ８１ － is represented by any one of the following chemical formulas 8D to 8F, B ８１ ＋ and A ８１ － is optionally linked through a carbon-carbon covalent bond; 【Chemistry 11】 In the above Chemical Formulae 8A to 8F, L ８１ and L ８２ each independently represents a single bond or CRR′; R and R′ are each independently hydrogen, deuterium, a halogen, a cyano group, a hydroxyl group, C １ -C ３０ Alkyl group, C １ -C ３０ Halogenated alkyl group, C １ -C ３０ Alkoxy group, C ３ -C ３０ Cycloalkyl group, or C ３ -C ３０ is a cycloalkoxy group, n81 and n82 each independently represent 1, 2, or 3; x81 is 0 or 1, R ８１ ~R ８４ each independently represents a C which may optionally contain a heteroatom; １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of R ８１ ~R ８４ adjacent two of may optionally be bonded to each other to form a fused ring; R ８５ and R ８６ is hydrogen; halogen; or C, which may optionally contain heteroatoms. １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

18. A step of applying the resist composition according to claim 14 onto a substrate to form a resist film; exposing at least a portion of the resist film to high energy radiation; and developing the exposed resist film using a developer.

19. 20. The method of claim 18, wherein the exposing step is performed by irradiating with ultraviolet light, deep ultraviolet light (DUV), extreme ultraviolet light (EUV), X-rays, gamma rays, electron beams (EB), and / or alpha rays.

20. The method further includes a step of heating the exposed resist film after the exposing step, The method of claim 18, wherein crosslinks are formed in the polymer during the heating step.

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